US6646147B2 - Process for the dissolution of copper metal - Google Patents

Process for the dissolution of copper metal Download PDF

Info

Publication number
US6646147B2
US6646147B2 US10/074,251 US7425102A US6646147B2 US 6646147 B2 US6646147 B2 US 6646147B2 US 7425102 A US7425102 A US 7425102A US 6646147 B2 US6646147 B2 US 6646147B2
Authority
US
United States
Prior art keywords
copper
process according
solution
monoethanolamine
dissolution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime, expires
Application number
US10/074,251
Other versions
US20030162986A1 (en
Inventor
Hugh W. Richardson
Gang Zhao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koppers Performance Chemicals Inc
Original Assignee
Phibro Tech Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Phibro Tech Inc filed Critical Phibro Tech Inc
Priority to US10/074,251 priority Critical patent/US6646147B2/en
Assigned to PHIBROTECH, INC. reassignment PHIBROTECH, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RICHARDSON, HUGH W., ZHAO, GANG
Priority to AT03739790T priority patent/ATE427952T1/en
Priority to MXPA04007806A priority patent/MXPA04007806A/en
Priority to CA 2476643 priority patent/CA2476643C/en
Priority to PCT/US2003/004368 priority patent/WO2003069025A2/en
Priority to CN038038900A priority patent/CN1633438B/en
Priority to DE60327061T priority patent/DE60327061D1/en
Priority to EP03739790A priority patent/EP1490375B1/en
Priority to AU2003216260A priority patent/AU2003216260B2/en
Publication of US20030162986A1 publication Critical patent/US20030162986A1/en
Priority to US10/660,795 priority patent/US6905531B2/en
Priority to US10/704,155 priority patent/US6905532B2/en
Publication of US6646147B2 publication Critical patent/US6646147B2/en
Application granted granted Critical
Assigned to WELLS FARGO FOOTHILL, INC. reassignment WELLS FARGO FOOTHILL, INC. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PHIBRO-TECH, INC.
Priority to US11/046,804 priority patent/US7476371B2/en
Assigned to WELLS FARGO FOOTHILL, INC. reassignment WELLS FARGO FOOTHILL, INC. AMENDMENT NUMBER ONE TO PATENT SECURITY AGREEMENT Assignors: PHIBRO-TECH, INC.
Priority to US11/980,524 priority patent/US20080175773A1/en
Assigned to OSMOSE, INC reassignment OSMOSE, INC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PHIBROTECH, INC., PHIBROWOOD, LLC
Assigned to CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT reassignment CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT INTELLECTUAL PROPERTY SECURITY AGREEMENT Assignors: OSMOSE, INC. (FORMERLY OSMOSE WOOD PRESERVING, INC.)
Assigned to CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT reassignment CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT INTELLECTUAL PROPERTY SECURITY AGREEMENT Assignors: OSMOSE, INC.
Assigned to PHIBRO-TECH, INC. reassignment PHIBRO-TECH, INC. RELEASE OF SECURITY INTEREST Assignors: WELLS FARGO FOOTHILL, INC.
Assigned to WELLS FARGO BANK, NATIONAL ASSOCIATION reassignment WELLS FARGO BANK, NATIONAL ASSOCIATION PATENT, TRADEMARK AND COPYRIGHT SECURITY AGREEMENT Assignors: CONCRETE PARTNERS, INC., KOPPERS ASIA LLC, KOPPERS CONCRETE PRODUCTS, INC., KOPPERS DELAWARE, INC., KOPPERS HOLDINGS INC., KOPPERS INC., KOPPERS VENTURES LLC, KOPPERS WORLD-WIDE VENTURES CORPORATION
Assigned to OSMOSE, INC. reassignment OSMOSE, INC. RELEASE OF SECURITY INTERST IN INTELLECTUAL PROPERTY Assignors: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
Assigned to OSMOSE, INC. (FORMERLY OSMOSE WOOD PRESERVING, INC.) reassignment OSMOSE, INC. (FORMERLY OSMOSE WOOD PRESERVING, INC.) RELEASE OF SECURITY INTEREST IN INTELLECTUAL PROPERTY Assignors: CREDIT SUISSE AG, CAYMAND ISLANDS BRANCH, AS COLLATERAL AGENT
Assigned to KOPPERS PERFORMANCE CHEMICALS INC reassignment KOPPERS PERFORMANCE CHEMICALS INC CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: OSMOSE, INC.
Assigned to KOPPERS PERFORMANCE CHEMICALS INC. reassignment KOPPERS PERFORMANCE CHEMICALS INC. CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE PATENT NUMBER 8221797 PREVIOUSLY RECORDED AT REEL: 034036 FRAME: 0363. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF NAME. Assignors: OSMOSE, INC.
Assigned to PNC BANK, NATIONAL ASSOCIATION reassignment PNC BANK, NATIONAL ASSOCIATION PATENT, TRADEMARK AND COPYRIGHT SECURITY AGREEMENT Assignors: CONCRETE PARTNERS, INC., KOPPERS ASIA LLC, KOPPERS CONCRETE PRODUCTS, INC., KOPPERS DELAWARE, INC., KOPPERS HOLDINGS INC., KOPPERS NZ LLC, KOPPERS PERFORMANCE CHEMICALS, INC., KOPPERS RAILROAD STRUCTURES INC., KOPPERS VENTURES INC., KOPPERS WORLD-WIDE VENTURES CORPORATION, KOPPERS, INC., KOPPERS-NEVADA LIMITED-LIABILITY COMPANY, WOOD PROTECTION LP, WOOD PROTECTION MANAGEMENT LLC
Adjusted expiration legal-status Critical
Assigned to KOPPERS INC. (F/K/A KOPPERS INDUSTRIES, INC.), KOPPERS DELAWARE, INC., KOPPERS UTILITY AND INDUSTRIAL PRODUCTS INC. (F/K/A COX INDUSTRIES, INC.), KOPPERS PERFORMANCE CHEMICALS INC. (F/K/A OSMOSE, INC.) reassignment KOPPERS INC. (F/K/A KOPPERS INDUSTRIES, INC.) RELEASE OF PATENT SECURITY INTERESTS Assignors: PNC BANK, NATIONAL ASSOCIATION
Assigned to KOPPERS DELAWARE, INC. (F/K/A KOPPERS INDUSTRIES OF DELAWARE, INC.), OSMOSE UTILITIES SERVICES, INC., KOPPERS INC. (F/K/A KOPPERS INDUSTRIES, INC), KOPPERS PERFORMANCE CHEMICALS INC. (F/K/A OSMOSE, INC.), KOPPERS PERFORMANCE CHEMICALS NEW ZEALAND LIMITED (F/K/A OSMOSE NEW ZEALAND) reassignment KOPPERS DELAWARE, INC. (F/K/A KOPPERS INDUSTRIES OF DELAWARE, INC.) RELEASE (REEL 033591 / FRAME 0020) Assignors: WELLS FARGO BANK, NATIONAL ASSOCIATION
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0056—Scrap treating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a process for the dissolution of copper metal. More particularly, the invention relates to a process for producing a copper-containing aqueous solution by dissolving copper in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (monoethanolammonium) 2 carbonate (HMEA) 2 CO 3 .
  • the copper-containing solutions may be formulated, for example, by dissolving copper in aqueous solutions containing alkyl amines or alkyl hydroxy amines, such as 2-hydroxyethylamine.
  • copper-containing solutions may be produced by reacting copper oxide with chromic acid and arsenous acid to produce a solution of the copper with chrome and arsenic. The solution is subsequently diluted with water and the resulting aqueous solution may be injected into wood under pressure.
  • CCA chromated copper arsenate
  • a new generation of pesticide is now emerging that appears to be efficacious, and which relies on the use of copper (in larger quantities than in the CCA) in combination with other pesticidal components, such as quaternary amines and triazoles.
  • the copper is typically applied as a solution of the monoethanolamine complex of copper carbonate or borate.
  • the commercial form of the copper concentrate usually contains about 100 to 130 g/l copper which is diluted with water prior to injection into the wood.
  • the copper complex is typically produced commercially by the dissolution of basic copper carbonate in a solution of monoethanolamine (MEA), followed by further carbonation or addition of boric acid.
  • MEA monoethanolamine
  • the reactions can be approximately represented by the following equations:
  • the present invention seeks to fill that need.
  • the present invention accordingly provides a process for producing a copper-containing aqueous solution, wherein a copper mass is dissolved in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (monoethanolammonium) 2 carbonate (HMEA) 2 CO 3 , the leach liquor being produced by partially carbonating the monoethanolamine.
  • copper-containing solution may be produced in 8-12 hours or less, more usually within about 8 hours or less.
  • FIG. 1 is a schematic depiction of a batch dissolver to be used for performing the present invention in a batch-wise manner
  • FIG. 2 is a plot showing the copper dissolution in the batch process
  • FIG. 3 is a plot showing the copper dissolution rate as a function of time
  • FIG. 4 is a schematic for continuous production of MEA complex of copper solution
  • FIG. 5 is a plot showing the copper dissolution rate versus air flow rate in a continuous process at pH 9.8;
  • FIG. 6 is a plot showing the copper dissolution rate versus air flow rate in a continuous process at pH 9.5;
  • FIG. 7 is a plot showing the copper dissolution rate as a function of pH.
  • a batch dissolver having a chamber 4 , with a false bottom 6 , and an air sparger 8 located below the false bottom.
  • the chamber is surrounded by a heating coil is 10 and has a top 12 through which extend a thermocouple 14 and an air inlet 16 .
  • the thermocouple is connected to a temperature control unit 18 and supplies heat to the heating coil 10 through conduit 20 .
  • Leach liquor 22 is circulated through the chamber by circulation pump 24 through lines 26 , 28 .
  • Copper metal 30 typically scrap copper, is present in the chamber and immersed in the leach liquor to enable the dissolution to occur.
  • copper as used herein means copper metal, including scrap copper, such as for example copper wire, copper clippings, copper tubing, copper cabling and/or copper plate, compounds of copper, such as copper oxide, and/or mixtures of copper metal and copper compounds.
  • copper mass refers to copper metal in a form which, when present in the chamber, is permeable to the leach liquor and which presents high surface area for contact with the leach liquor to thereby expedite dissolution of the copper.
  • the copper mass may be present for example as a three-dimensional open permeable network, such as a bale of scrap copper comprised of copper wire, copper tubing, copper cabling, copper plates, providing voids between the copper pieces to allow free flow and maximum contact of the leach liquor with the copper.
  • a bale may have a volume of for example about 25-100 cubic fee.
  • the copper mass may be present in the chamber as smaller irregular shaped pieces resembling “popcorn”(“blister shot”) having an average dimension of about 1-3′′, which allow for good permeation of the leach liquor between and around the copper pieces to expedite dissolution thereof.
  • the ratio of copper surface area to volume of leach liquor for this process versus a standard agitated reactor is about 10-20:1, for example about 15:1.
  • the copper mass is dissolved in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (HMEA) 2 CO 3 .
  • an oxidant in an aqueous leach liquor containing monoethanolamine and (HMEA) 2 CO 3 .
  • the air flow SCFH ranges from about 2-20, for example 3-10. The air flow SCFH will increase as the volume of the chamber increases.
  • the leach liquor is produced by partially carbonating the monoethanolamine and may be generated externally of the dissolver or in situ in the chamber through addition of carbon dioxide to the monoethanolamine/water solution by sparging or bubbling into the chamber.
  • the leach liquor is produced externally of the chamber and introduced into the chamber into contact with the copper as required, or re-circulated as necessary.
  • the amount of carbon dioxide introduced during the process is controlled such that partial carbonation occurs to form (HMEA) 2 CO 3 .
  • the carbon dioxide is present in an amount of about 5-30% by weight, for example about 8-12% by weight.
  • the MEA is usually present in an amount of about 30-40 wt %, more usually 35-38 wt%.
  • a typical aqueous leach solution of comprises about 36 wt% MEA and about 10% by weight carbon dioxide.
  • the monoethanolamine complex of copper carbonate solutions are typically prepared by dissolving the copper mass in a monoethanolamine/CO 2 /H 2 O solution.
  • the dissolution may be carried out in a batch dissolver (see FIG. 1 ), or may be performed as a continuous process in towers packed with copper (see FIG. 4 ).
  • the copper and MEA/CO 2 /H 2 O solution are charged into the dissolver, and the circulation pump, air-flow and temperature controller are actuated. Examples of conditions are given in Table 3 below.
  • the present inventors have discovered that it is not necessary to utilize precursors, such as copper carbonate which is expensive.
  • the dissolution of the copper metal may be achieved in the presence of MEA, (HMEA) 2 CO 3 and an oxidant at elevated temperature, without the need for the addition of ammonium compounds such as ammonium hydroxide, fungicidal anions, polyamines, carboxylic acids, alkali metal hydroxides such as sodium hydroxide, and/or alcohol-based solvents.
  • the dissolution of the copper metal is performed in the presence of an oxidant.
  • an oxidant is an air and/or oxygen, most usually air sparging.
  • the leach solution is typically re-circulated in the reactor. Most typically, the re-circulation is carried out at a constant rate, and may be, for example, a constant rate of about one-tenth of the leach solution volume per minute.
  • the process may be carried out at atmospheric pressure and at a temperature of 25-100° C., for example 45-65° C. Typically, the temperature is maintained at 45-55° C.
  • the pH is typically maintained in the basic region, i.e. greater than 7, and is usually from about 8.0-11.3,more usually 9-10.
  • the pH is usually maintained by addition of carbon dioxide as acid, or MEA as base.
  • the reaction proceeds slowly where there is a small surface area of copper available to contact the leach solution. For example, if the contact area of the copper metal to leach solution is doubled, the rate of the process doubles assuming adequate air-distribution.
  • FIG. 1 shows a conventional batch dissolver used for the batch-wise operation.
  • FIG. 4 shows a continuous dissolution process.
  • the conditions used in the batch experiments are given in Table 1. The temperature was maintained at 45-55° C.
  • the leach solutions are typically re-circulated in the reactor. Most typically, the re-circulation is carried out at a constant rate of about one-tenth
  • the solution concentration of copper (g/l) as a function of dissolution time is shown in Table 2:
  • FIG. 4 is a schematic for the continuous production of MEA complex in solution.
  • the dissolver generally referenced 32 , has a chamber 34 , with a false bottom 36 , and an air sparger 38 located below the false bottom.
  • the chamber is surrounded by a heating coil 40 and has a top 42 through which extend a thermocouple 44 and an outlet 46 .
  • the thermocouple is connected to a temperature control unit 48 and supplies heat to the heating coil 40 through conduit 50 .
  • Leach liquor 52 is circulated through the chamber by circulation pumps 54 through lines 56 , 58 .
  • a copper mass 60 is present in the chamber and immersed in the leach liquor to enable the dissolution to occur.
  • the system is also provided with a pH control 62 connected to a gravity controller 64 into which carbon dioxide is admitted from tank 66 .
  • Carbon dioxide off-gas is directed through line 46 to a carbon dioxide scrubber 68 .
  • Carbon dioxide from the scrubber 68 is the fed to chamber 70 containing MEA and water which is pumped via pump 72 to chamber 34 .
  • the system also comprises an oxidation chamber 74 into which oxygen is admitted via line 76 .
  • Product enters at line 78 and following oxidation exits via line 80 and is transferred to product storage.
  • Monoethanolamine complex of copper carbonate solutions were prepared by dissolving a copper metal mass in monoethanolamine/CO 2 /H 2 O solution in the batch dissolver in the presence of air sparging and at an elevated temperature.
  • FIG. 1 shows a conventional batch dissolver used for the batch-wise operation.
  • FIG. 2 is a plot showing the copper dissolution in the batch process
  • FIG. 3 is a plot showing the copper dissolution rate as a function of time.
  • a continuous dissolver assembly (see FIG. 4) was used in the experiments described below.
  • the assembly includes a one-liter size packed-tower dissolver (used in the batch dissolving experiments described above); gravity controller, a temperature controller, a pH monitor, an air flow meter, a circulation pump and a pump for simultaneous withdraw and replenish of solutions.
  • the gravity controller held about 1 liter of the product solution.
  • the solution in the assembly was circulated between the gravity controller and the dissolver at a constant rate of 325 ml/min. Occasionally, CO 2 gas was bubbled through the bottom of the gravity control chamber to adjust the pH of the solution.
  • the reaction temperature and specific gravity were controlled at 50 ⁇ 2° C. and 1.271 ⁇ 0.001 g/ml, respectively.
  • FIG. 5 is a plot showing the copper dissolution rate versus air flow rate in a continuous process at pH 9.8
  • FIG. 6 is a plot showing the copper dissolution rate versus air flow rate in a continuous process at pH 9.5
  • FIG. 7 is a plot showing the copper dissolution rate as a function of pH.

Abstract

Process for producing a copper-containing aqueous solution, in which a copper mass is dissolved in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (HMEA)2CO3. The leach liquor is produced by partially carbonating the monoethanolamine.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for the dissolution of copper metal. More particularly, the invention relates to a process for producing a copper-containing aqueous solution by dissolving copper in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (monoethanolammonium)2 carbonate (HMEA)2CO3.
2. Description of the Prior Art
It is known to employ copper-containing aqueous solutions as biocidal fluids, for example, for the pressure treatment of lumber and for water purification. Examples of such fluids and uses thereof may be found, for example, in U.S. Pat. No. 4,929,454 and U.S. Pat. No. 6,294,071. The copper-containing solutions may be formulated, for example, by dissolving copper in aqueous solutions containing alkyl amines or alkyl hydroxy amines, such as 2-hydroxyethylamine.
Alternatively, copper-containing solutions may be produced by reacting copper oxide with chromic acid and arsenous acid to produce a solution of the copper with chrome and arsenic. The solution is subsequently diluted with water and the resulting aqueous solution may be injected into wood under pressure.
This chromated copper arsenate (“CCA”) is the primary additive used in the treatment of wood against termite and other biological infestation. Although the CCA is very effective, it has come under increased pressure because of the environmental concerns associated with chromium and arsenic.
A new generation of pesticide is now emerging that appears to be efficacious, and which relies on the use of copper (in larger quantities than in the CCA) in combination with other pesticidal components, such as quaternary amines and triazoles. The copper is typically applied as a solution of the monoethanolamine complex of copper carbonate or borate. The commercial form of the copper concentrate usually contains about 100 to 130 g/l copper which is diluted with water prior to injection into the wood.
The copper complex is typically produced commercially by the dissolution of basic copper carbonate in a solution of monoethanolamine (MEA), followed by further carbonation or addition of boric acid. The reactions can be approximately represented by the following equations:
CuCO3Cu(OH)2+7MEA→ Cu(MEA)3.5CO3+Cu(MEA)3.5(OH)2
Cu(MEA)3.5(OH)2+CO2(or Boric acid)→ Cu(MEA)3.5CO3+H2O
The production of the copper carbonate precursor has its own production and raw material costs, and a brine waste is generated which gives rise to environmental concerns. A more efficient process might be to produce the complex without the aid of an isolated precursor. It is known from the prior art that ammonia and carbon dioxide in water can be used to dissolve copper metal with oxygen from air as the oxidant. This is represented by the following equation:
Cu+2NH3+(NH4)2CO3+1/2O2→ Cu(NH 3) 4CO3+H2O
The reaction proceeds well and has been the basis for copper dissolution in several commercial facilities. However, if the ammonia is not initially carbonated, the kinetics are very poor which makes the process unattractive from a commercial standpoint.
A need exists for a more efficient process for producing copper-containing aqueous solutions, suitable for use in the wood-treatment industry. The present invention seeks to fill that need.
SUMMARY OF THE INVENTION
It has been discovered, according to the present invention, that it is possible to efficiently produce copper-containing solutions directly without initially producing or isolating a precursor such as copper carbonate. The present invention accordingly provides a process for producing a copper-containing aqueous solution, wherein a copper mass is dissolved in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (monoethanolammonium)2 carbonate (HMEA)2CO3, the leach liquor being produced by partially carbonating the monoethanolamine. According to the process, copper-containing solution may be produced in 8-12 hours or less, more usually within about 8 hours or less.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will now be described in more detail with reference to the accompanying drawings, in which:
FIG. 1 is a schematic depiction of a batch dissolver to be used for performing the present invention in a batch-wise manner;
FIG. 2 is a plot showing the copper dissolution in the batch process;
FIG. 3 is a plot showing the copper dissolution rate as a function of time;
FIG. 4 is a schematic for continuous production of MEA complex of copper solution;
FIG. 5 is a plot showing the copper dissolution rate versus air flow rate in a continuous process at pH 9.8;
FIG. 6 is a plot showing the copper dissolution rate versus air flow rate in a continuous process at pH 9.5;
FIG. 7 is a plot showing the copper dissolution rate as a function of pH.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, there is shown a batch dissolver, generally referenced 2, having a chamber 4, with a false bottom 6, and an air sparger 8 located below the false bottom. The chamber is surrounded by a heating coil is 10 and has a top 12 through which extend a thermocouple 14 and an air inlet 16. The thermocouple is connected to a temperature control unit 18 and supplies heat to the heating coil 10 through conduit 20. Leach liquor 22 is circulated through the chamber by circulation pump 24 through lines 26, 28. Copper metal 30, typically scrap copper, is present in the chamber and immersed in the leach liquor to enable the dissolution to occur.
The term “copper” as used herein means copper metal, including scrap copper, such as for example copper wire, copper clippings, copper tubing, copper cabling and/or copper plate, compounds of copper, such as copper oxide, and/or mixtures of copper metal and copper compounds.
The term “copper mass” as used herein refers to copper metal in a form which, when present in the chamber, is permeable to the leach liquor and which presents high surface area for contact with the leach liquor to thereby expedite dissolution of the copper. The copper mass may be present for example as a three-dimensional open permeable network, such as a bale of scrap copper comprised of copper wire, copper tubing, copper cabling, copper plates, providing voids between the copper pieces to allow free flow and maximum contact of the leach liquor with the copper. A bale may have a volume of for example about 25-100 cubic fee. Alternatively, the copper mass may be present in the chamber as smaller irregular shaped pieces resembling “popcorn”(“blister shot”) having an average dimension of about 1-3″, which allow for good permeation of the leach liquor between and around the copper pieces to expedite dissolution thereof. Typically, the ratio of copper surface area to volume of leach liquor for this process versus a standard agitated reactor is about 10-20:1, for example about 15:1.
According to the process, the copper mass is dissolved in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (HMEA)2CO3. Typically, for a 1 liter chamber, the air flow SCFH ranges from about 2-20, for example 3-10. The air flow SCFH will increase as the volume of the chamber increases.
The leach liquor is produced by partially carbonating the monoethanolamine and may be generated externally of the dissolver or in situ in the chamber through addition of carbon dioxide to the monoethanolamine/water solution by sparging or bubbling into the chamber. Usually, the leach liquor is produced externally of the chamber and introduced into the chamber into contact with the copper as required, or re-circulated as necessary.
The equation that represents the overall reaction is as follows:
Cu+1.5MEA+(HMEA)2CO3+1/2O2→ Cu(MEA)3.5CO3+H2O
The equation that represents the in situ or external partial carbonation of the monoethanolamine is as follows:
3.5MEA+CO2+H2O→1.5MEA+(HMEA)2CO3.
The amount of carbon dioxide introduced during the process is controlled such that partial carbonation occurs to form (HMEA)2CO3. Typically, the carbon dioxide is present in an amount of about 5-30% by weight, for example about 8-12% by weight.
The MEA is usually present in an amount of about 30-40 wt %, more usually 35-38 wt%. A typical aqueous leach solution of comprises about 36 wt% MEA and about 10% by weight carbon dioxide.
The monoethanolamine complex of copper carbonate solutions are typically prepared by dissolving the copper mass in a monoethanolamine/CO2/H2O solution. The dissolution may be carried out in a batch dissolver (see FIG. 1), or may be performed as a continuous process in towers packed with copper (see FIG. 4). Typically, the copper and MEA/CO2/H2O solution are charged into the dissolver, and the circulation pump, air-flow and temperature controller are actuated. Examples of conditions are given in Table 3 below.
The present inventors have discovered that it is not necessary to utilize precursors, such as copper carbonate which is expensive. The dissolution of the copper metal may be achieved in the presence of MEA, (HMEA)2CO3 and an oxidant at elevated temperature, without the need for the addition of ammonium compounds such as ammonium hydroxide, fungicidal anions, polyamines, carboxylic acids, alkali metal hydroxides such as sodium hydroxide, and/or alcohol-based solvents.
The dissolution of the copper metal is performed in the presence of an oxidant. Typically the oxidant is an air and/or oxygen, most usually air sparging.
The leach solution is typically re-circulated in the reactor. Most typically, the re-circulation is carried out at a constant rate, and may be, for example, a constant rate of about one-tenth of the leach solution volume per minute.
The process may be carried out at atmospheric pressure and at a temperature of 25-100° C., for example 45-65° C. Typically, the temperature is maintained at 45-55° C.
The pH is typically maintained in the basic region, i.e. greater than 7, and is usually from about 8.0-11.3,more usually 9-10.The pH is usually maintained by addition of carbon dioxide as acid, or MEA as base.
The reaction proceeds slowly where there is a small surface area of copper available to contact the leach solution. For example, if the contact area of the copper metal to leach solution is doubled, the rate of the process doubles assuming adequate air-distribution.
It has been found that an aerated packed tower containing copper metal and circulating leach liquor is the most preferred method for commercial purposes. The advantage of using a packed tower is that it maintains a relatively high surface area to solution volume of copper metal.
According to another embodiment of the present invention, it is possible to utilize a reactor that contains a bed of copper and can be rotated while being heated and aerated.
Dissolving studies were conducted either batch-wise or continuously. FIG. 1 shows a conventional batch dissolver used for the batch-wise operation. FIG. 4 shows a continuous dissolution process. The conditions used in the batch experiments are given in Table 1. The temperature was maintained at 45-55° C.
TABLE 1
Leach Solution
EXP. # ID Amine, % CO2, % Volume, ml Cu Charge, g
1 MEA-CO2 36.7 12 600 400
solution
2 MEA-CO2 35.9 13 200 200
solution
The leach solutions are typically re-circulated in the reactor. Most typically, the re-circulation is carried out at a constant rate of about one-tenth The solution concentration of copper (g/l) as a function of dissolution time is shown in Table 2:
TABLE 2
Dissolution Time, hour
EXP. #
1 2 3 4 5 6 7 8
1 3.7 15.7 41.3 67.8 88.2 100.3
2 5.4 16.8 55.7 85.1 102.5 119.2 126.4 136.1
In experiments 1 and 2 reported above, average copper dissolution rates of about 17 g/l-hr were achieved over the course of the experiments. At those rates, the process is viable commercially. Raw material costs, processing costs and waste are significantly reduced over the conventional process using copper carbonate.
FIG. 4 is a schematic for the continuous production of MEA complex in solution. The dissolver, generally referenced 32, has a chamber 34, with a false bottom 36, and an air sparger 38 located below the false bottom. The chamber is surrounded by a heating coil 40 and has a top 42 through which extend a thermocouple 44 and an outlet 46. The thermocouple is connected to a temperature control unit 48 and supplies heat to the heating coil 40 through conduit 50. Leach liquor 52 is circulated through the chamber by circulation pumps 54 through lines 56, 58. A copper mass 60 is present in the chamber and immersed in the leach liquor to enable the dissolution to occur. The system is also provided with a pH control 62 connected to a gravity controller 64 into which carbon dioxide is admitted from tank 66. Carbon dioxide off-gas is directed through line 46 to a carbon dioxide scrubber 68. Carbon dioxide from the scrubber 68 is the fed to chamber 70 containing MEA and water which is pumped via pump 72 to chamber 34. The system also comprises an oxidation chamber 74 into which oxygen is admitted via line 76. Product enters at line 78 and following oxidation exits via line 80 and is transferred to product storage.
EXAMPLES
Examples of the process according to the present invention will now be described.
EXAMPLE 1
Batch Preparation of Monoethanolamine Complex of Copper Carbonate
Monoethanolamine complex of copper carbonate solutions were prepared by dissolving a copper metal mass in monoethanolamine/CO2/H2O solution in the batch dissolver in the presence of air sparging and at an elevated temperature. FIG. 1 shows a conventional batch dissolver used for the batch-wise operation.
Three experiments were conducted using the batch dissolver shown in FIG. 1. In each experiment, about 1200 g copper and 1 liter MEA-CO2-H2O solution were charged into the dissolver. The circulation pump, airflow and temperature controller were then started. The experimental conditions are given in Table 3.
TABLE 3
Air Circulation
Exp MEA-H2O—CO2 Solution Flow Tempera- Rate
ID MEA/H2O1 % CO2 Sp.G SCFH ture ° C. ml/min
1 0.900/1.00 13.7 1.165 6.0 51 ± 1 182
2 0.733/1.00 14.1 1.160 6.0 51 ± 1 182
3 0.900/1.00 13.7 1.165 6.0 76 ± 1 182
1. Weight ratio
When temperature reached the target temperature, the first sample of each batch was taken for analysis, and the timer was started. Complete results of these three dissolving batches are shown below, and are presented in FIGS. 2 and 3. FIG. 2 is a plot showing the copper dissolution in the batch process, and FIG. 3 is a plot showing the copper dissolution rate as a function of time.
TABLE 4
Batch Dissolving - Experiment #1
Time, hour % Cu pH Sp.G. Copper, g/L
0 0.16 8.8 1.165 1.9
1 2.155 9.6 1.175 25.3
2 4.85 N/a 1.205 58.4
3 6.73  9.45 1.228 82.6
4 7.66 9.6 1.239 94.9
5 8.36 9.6 1.251 104.5
6 9.23 9.6 1.262 116.5
7 9.79 N/a 1.271 124.4
8 10.32  9.65 1.277 131.8
TABLE 5
Batch Dissolving - Experiment #2
Time, hour % Cu pH Sp.G. Copper, g/L
0 1.17 9.00 1.170 13.7
1 3.5 9.25 1.180 41.3
2 6.07 9.30 1.204 73.1
3 7.37 9.37 1.223 90.1
4
5 9.29 9.55 1.250 116.1
6 9.76 9.65 1.258 122.7
7 10.23 9.65 1.265 129.4
8 10.63 9.65 1.267 134.7
TABLE 6
Batch Dissolving - Experiment #3
Time, hour % Cu pH Sp.G. Copper, g/L
0 1.175 9.45 1.175 13.8
1 7.054 9.80 1.208 85.2
2 8.661 10.0 1.237 107.1
3 10.11 10.2 1.251 126.4
4 10.99 10.3 1.267 139.2
EXAMPLE 2
A continuous dissolver assembly (see FIG. 4) was used in the experiments described below. The assembly includes a one-liter size packed-tower dissolver (used in the batch dissolving experiments described above); gravity controller, a temperature controller, a pH monitor, an air flow meter, a circulation pump and a pump for simultaneous withdraw and replenish of solutions. The gravity controller held about 1 liter of the product solution. The solution in the assembly was circulated between the gravity controller and the dissolver at a constant rate of 325 ml/min. Occasionally, CO2 gas was bubbled through the bottom of the gravity control chamber to adjust the pH of the solution. In all experiments described below, the reaction temperature and specific gravity were controlled at 50±2° C. and 1.271±0.001 g/ml, respectively. During a continuous dissolving experiment, copper is continuously dissolved and results in a graduate increase of the specific gravity of the copper-containing solution. When the gravity reaches a pre-set value, i.e. 1.272, it triggers a pump to withdraw the product solution and replenish MEA-CO2 solution simultaneously. The composition of the MEA-CO2 solution used in all continuous dissolving experiments is the same as that of Exp#1 of batch process (Table 3). The dissolver was charged on a daily basis with 1″ pieces of 11-13 AWG scrap copper wires and maintained a total copper loading of 1100-1200 grams at any given period of the experiments. Results are shown below in Table 7 along with the experimental conditions used, and are also presented in FIGS. 5-7. FIG. 5 is a plot showing the copper dissolution rate versus air flow rate in a continuous process at pH 9.8, FIG. 6 is a plot showing the copper dissolution rate versus air flow rate in a continuous process at pH 9.5 and FIG. 7 is a plot showing the copper dissolution rate as a function of pH.
TABLE 7
Conditions and Results of Continuous Dissolving Experiments
Copper
Duration Air Flow MEA-Cu—CO2 Solution Dissolution
Hour pH SCFH Volume, ml Copper, % g/l/hr
2.13 9.8 6.0 125 10.61 7.91
2.13 9.8 3.0 85 10.41 5.28
0.65 9.8 8.0 41 10.41 8.35
3.35 9.5 6.0 183 10.15 7.05
0.64 9.5 10.0 46 10.15 9.27
0.78 9.5 4.5 35 10.15 5.79
4.1 9.1 6.0 123 9.575 3.65
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims (13)

What is claimed is:
1. A process for producing a copper-containing aqueous solution, comprising dissolving a copper mass in the presence of an oxidant in an aqueous leach liquor containing monoethanolamine and (HMEA)2CO3, wherein said leach liquor is produced by partially carbonating the monoethanolamine.
2. A process according to claim 1, wherein said oxidant is selected from the group consisting of air and oxygen.
3. A process according to claim 1, wherein the process is carried out at a temperature of 40-80° C.
4. A process according to claim 3, wherein said temperature is 45-55° C.
5. A process according to claim 1, wherein said leach solution is re-circulated at a constant rate.
6. A process according to claim 5, wherein said recirculation is carried out at a constant rate of about one tenth of the leach solution volume per minute.
7. A process according to claim, wherein the reaction is represented by the following equation:
Cu+1.5MEA+(HMEA)2CO3+1/2O2→ Cu(MEA)3.5CO3+H2O.
8. A process according to claim 1, wherein said partial carbonating of said the monoethanolamine is according to the following equation:
3.5MEA+CO2+H2O→1.5MEA+(HMEA)2CO3.
9. A process according to claim 1, wherein the carbon dioxide is present in an amount of about 5-30% by weight.
10. A process according to claim 1, wherein the pH is 8.0-11-3.
11. A process according to claim 1, performed as a batch process.
12. A process according to claim 1, wherein the average copper dissolution rate is about 17 g/l-hour.
13. A process according to claim 1, performed as a continuous process.
US10/074,251 2002-02-14 2002-02-14 Process for the dissolution of copper metal Expired - Lifetime US6646147B2 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
US10/074,251 US6646147B2 (en) 2002-02-14 2002-02-14 Process for the dissolution of copper metal
AU2003216260A AU2003216260B2 (en) 2002-02-14 2003-02-14 Process for the dissolution of copper metal
MXPA04007806A MXPA04007806A (en) 2002-02-14 2003-02-14 Process for the dissolution of copper metal.
CA 2476643 CA2476643C (en) 2002-02-14 2003-02-14 Process for the dissolution of copper metal
AT03739790T ATE427952T1 (en) 2002-02-14 2003-02-14 METHOD FOR DISSOLVING COPPER METAL
PCT/US2003/004368 WO2003069025A2 (en) 2002-02-14 2003-02-14 Process for the dissolution of copper metal
CN038038900A CN1633438B (en) 2002-02-14 2003-02-14 Process for the dissolution of copper metal
DE60327061T DE60327061D1 (en) 2002-02-14 2003-02-14 METHOD FOR RESOLVING COPPER METAL
EP03739790A EP1490375B1 (en) 2002-02-14 2003-02-14 Process for the dissolution of copper metal
US10/660,795 US6905531B2 (en) 2002-02-14 2003-09-12 Process for the dissolution of copper metal
US10/704,155 US6905532B2 (en) 2002-02-14 2003-11-10 Process for the dissolution of copper metal
US11/046,804 US7476371B2 (en) 2002-02-14 2005-02-01 Dissolution of copper metal in aqueous alkanolamine to form copper containing aqueous solution
US11/980,524 US20080175773A1 (en) 2002-02-14 2007-10-31 Process for the dissolution of copper metal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/074,251 US6646147B2 (en) 2002-02-14 2002-02-14 Process for the dissolution of copper metal

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US10/660,795 Continuation US6905531B2 (en) 2002-02-14 2003-09-12 Process for the dissolution of copper metal
US10/704,155 Continuation-In-Part US6905532B2 (en) 2002-02-14 2003-11-10 Process for the dissolution of copper metal

Publications (2)

Publication Number Publication Date
US20030162986A1 US20030162986A1 (en) 2003-08-28
US6646147B2 true US6646147B2 (en) 2003-11-11

Family

ID=27732362

Family Applications (3)

Application Number Title Priority Date Filing Date
US10/074,251 Expired - Lifetime US6646147B2 (en) 2002-02-14 2002-02-14 Process for the dissolution of copper metal
US10/660,795 Expired - Lifetime US6905531B2 (en) 2002-02-14 2003-09-12 Process for the dissolution of copper metal
US10/704,155 Expired - Lifetime US6905532B2 (en) 2002-02-14 2003-11-10 Process for the dissolution of copper metal

Family Applications After (2)

Application Number Title Priority Date Filing Date
US10/660,795 Expired - Lifetime US6905531B2 (en) 2002-02-14 2003-09-12 Process for the dissolution of copper metal
US10/704,155 Expired - Lifetime US6905532B2 (en) 2002-02-14 2003-11-10 Process for the dissolution of copper metal

Country Status (9)

Country Link
US (3) US6646147B2 (en)
EP (1) EP1490375B1 (en)
CN (1) CN1633438B (en)
AT (1) ATE427952T1 (en)
AU (1) AU2003216260B2 (en)
CA (1) CA2476643C (en)
DE (1) DE60327061D1 (en)
MX (1) MXPA04007806A (en)
WO (1) WO2003069025A2 (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040191143A1 (en) * 2002-02-14 2004-09-30 Richardson Hugh W. Process for the dissolution of copper metal
US20040258768A1 (en) * 2003-06-17 2004-12-23 Richardson H. Wayne Particulate wood preservative and method for producing same
US20040258838A1 (en) * 2003-06-17 2004-12-23 Richardson H. Wayne Method for preserving wood materials using precipitated copper compounds
WO2005051961A1 (en) * 2003-11-19 2005-06-09 Arch Chemicals, Inc. Methods for producing copper ethanolamine solutions
US20050130866A1 (en) * 2002-02-14 2005-06-16 Richardson Hugh W. Process for the dissolution of copper metal
US20060062926A1 (en) * 2004-05-17 2006-03-23 Richardson H W Use of sub-micron copper salt particles in wood preservation
US20060078686A1 (en) * 2004-10-08 2006-04-13 Hodge Robert L Penetration of copper-ethanolamine complex in wood
US20060236813A1 (en) * 2005-04-20 2006-10-26 Gang Zhao Production of fine particle copper powders
US20070207076A1 (en) * 2006-03-06 2007-09-06 Osmose Inc. Method of preparing metal-containing wood preserving compositions
US20080175773A1 (en) * 2002-02-14 2008-07-24 Richardson H Wayne Process for the dissolution of copper metal
CN1882595B (en) * 2003-11-19 2011-06-08 阿奇化工公司 Methods for producing copper ethanolamine solutions
US8158208B2 (en) 2004-05-17 2012-04-17 Osmose, Inc. Method of preserving wood by injecting particulate wood preservative slurry
US8460759B2 (en) 2003-04-09 2013-06-11 Osmose, Inc. Micronized wood preservative formulations
US8637089B2 (en) 2003-04-09 2014-01-28 Osmose, Inc. Micronized wood preservative formulations
US8747908B2 (en) 2003-04-09 2014-06-10 Osmose, Inc. Micronized wood preservative formulations
US9775350B2 (en) 2004-10-14 2017-10-03 Koppers Performance Chemicals Inc. Micronized wood preservative formulations in organic carriers

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050265893A1 (en) 2004-05-13 2005-12-01 Leach Robert M Compositions and methods for treating cellulose-based materials with micronized additives
US20060257578A1 (en) * 2003-04-09 2006-11-16 Jun Zhang Micronized wood preservative formulations comprising boron compounds
US20080131666A1 (en) * 2003-07-31 2008-06-05 Fox Roger F Penetration improvement of copper amine solutions into dried wood by addition of carbon dioxide
US20050107467A1 (en) * 2003-10-17 2005-05-19 Richardson H. W. Methods for producing and using a Cu(I)-based wood preservative
US20050152994A1 (en) * 2003-12-08 2005-07-14 Leach Robert M. Composition and process for coloring and preserving wood
US20070131136A1 (en) * 2004-04-27 2007-06-14 Osmose, Inc. Composition And Process For Coloring Wood
AU2005237592A1 (en) * 2004-04-27 2005-11-10 Osmose, Inc. Micronized organic preservative formulations
US20060147632A1 (en) * 2004-04-27 2006-07-06 Jun Zhang Composition and process for coloring and preserving wood
US20060086284A1 (en) * 2004-10-14 2006-04-27 Jun Zhang Non-alkaline micronized wood preservative formulations
US20060276468A1 (en) * 2005-05-12 2006-12-07 Blow Derek P Wood preservative formulations comprising Imazalil
CA2616035A1 (en) * 2005-07-21 2007-02-01 Osmose, Inc. Compositions and methods for wood preservation
WO2007053252A1 (en) * 2005-11-01 2007-05-10 Osmose, Inc. Method of preparing metal-containing wood preserving compositions
US7411080B2 (en) * 2006-05-19 2008-08-12 Phibro-Tech, Inc. Direct synthesis of copper carbonate
US7632567B1 (en) 2006-08-31 2009-12-15 Osmose, Inc. Micronized wood preservative formulations comprising copper and zinc
US20080175913A1 (en) * 2007-01-09 2008-07-24 Jun Zhang Wood preservative compositions comprising isothiazolone-pyrethroids
US20090162410A1 (en) * 2007-12-21 2009-06-25 Jun Zhang Process for preparing fine particle dispersion for wood preservation
WO2009114171A2 (en) * 2008-03-14 2009-09-17 Union Carbide Chemicals & Plastics Technology Llc Hybrid strategies for reducing leaching of metal biocides from biodegradable substrates
US20090324481A1 (en) * 2008-06-27 2009-12-31 Jeff Miller Low energy method of preparing basic copper carbonates
TWI552960B (en) * 2012-04-25 2016-10-11 昶昕實業股份有限公司 Processes for dissolving copper and preparing copper salts
CN103667704B (en) * 2012-09-17 2015-10-28 中国科学院化学研究所 The metal of separating waste, worn printed wiring base board and nonmetallic method
TW201532714A (en) * 2014-02-21 2015-09-01 Co Tech Copper Foil Corp Method and apparatus for producing copper oxide therewith
WO2016132526A1 (en) * 2015-02-20 2016-08-25 株式会社島津製作所 Device for pretreatment of specimen and analyzer equipped therewith, and method for pretreatment of specimen
US10167202B2 (en) * 2016-02-23 2019-01-01 King Abdullah University Of Science And Technology Enhanced metal recovery through oxidation in liquid and/or supercritical carbon dioxide
FR3092727B1 (en) * 2019-02-19 2023-05-12 Upl Ltd Process for the preparation of copper compounds
CN114171654B (en) * 2021-12-08 2022-12-20 聚灿光电科技（宿迁）有限公司 Method for preparing electrode pattern
WO2023154469A1 (en) 2022-02-11 2023-08-17 Troy Technology Ii, Inc. Stabilized copper-amine donor aqueous solution with improved penetration and anti-leaching capabilities

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4929454A (en) * 1981-02-05 1990-05-29 Domtar Inc. Wood treatment composition
US5084201A (en) * 1989-11-14 1992-01-28 Akzo N.V. Soluble copper amino alkoxides
US5304666A (en) * 1988-07-01 1994-04-19 E. I. Du Pont De Nemours And Company Process for making superconductors and their precursors
US6294071B1 (en) * 2000-01-07 2001-09-25 Huntsman Petrochemical Corporation Methods of forming copper solutions

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US624071A (en) * 1899-05-02 Gas-burning heater
US2377966A (en) 1943-04-10 1945-06-12 Girdler Corp Stabilization of monoethanolamine solutions
US3375713A (en) 1966-03-28 1968-04-02 Marcius N. Gover Internal combustion engine ignition system distributor make and break analyzing apparatus
US3929598A (en) 1972-08-14 1975-12-30 Anaconda Co Recovery of copper and zinc from low-grade non-ferrous materials
US3930834A (en) 1974-01-14 1976-01-06 Applied Biochemists, Inc. Algaecidal composition
US3936294A (en) 1974-08-28 1976-02-03 Childress Kenneth A Reagent for zinc ore and method of utilizing same
US4324578A (en) * 1977-09-15 1982-04-13 Applied Biochemists, Inc. Method of preparing a copper complex for use as an algaecide
US4622248A (en) 1984-04-04 1986-11-11 Osmose Wood Preserving Co. Of America, Inc. Preservative composition for wood
US4578162A (en) 1984-05-29 1986-03-25 The Dow Chemical Company Method for dissolving copper in the presence of iron
US5078912A (en) 1985-06-07 1992-01-07 Dr. Wolman Gmbh Wood preservative
US4808407A (en) 1987-08-14 1989-02-28 Mooney Chemicals, Inc. Water-soluble copper salts
DE4033419A1 (en) 1990-10-20 1992-04-23 Wolman Gmbh Dr POLYMOUS NITROGEN COMPOUNDS AND METAL FIXING SAEURS CONTAINING WOOD PROTECTION AGENTS
US5431776A (en) 1993-09-08 1995-07-11 Phibro-Tech, Inc. Copper etchant solution additives
CA2262186A1 (en) * 1998-03-27 1999-09-27 Gb Biosciences Corporation Copper dissolver process
US6484883B1 (en) 2000-10-18 2002-11-26 Phibro-Tech Inc. Use of cupric chloride in zinc flotation
US6646147B2 (en) * 2002-02-14 2003-11-11 Phibrotech, Inc. Process for the dissolution of copper metal
US6843837B2 (en) 2002-07-26 2005-01-18 Osmose, Inc. Polymeric wood preservative compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4929454A (en) * 1981-02-05 1990-05-29 Domtar Inc. Wood treatment composition
US5304666A (en) * 1988-07-01 1994-04-19 E. I. Du Pont De Nemours And Company Process for making superconductors and their precursors
US5084201A (en) * 1989-11-14 1992-01-28 Akzo N.V. Soluble copper amino alkoxides
US6294071B1 (en) * 2000-01-07 2001-09-25 Huntsman Petrochemical Corporation Methods of forming copper solutions

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050130866A1 (en) * 2002-02-14 2005-06-16 Richardson Hugh W. Process for the dissolution of copper metal
US20040191143A1 (en) * 2002-02-14 2004-09-30 Richardson Hugh W. Process for the dissolution of copper metal
US7476371B2 (en) 2002-02-14 2009-01-13 Phibro-Tech, Inc. Dissolution of copper metal in aqueous alkanolamine to form copper containing aqueous solution
US20050034563A1 (en) * 2002-02-14 2005-02-17 Phibrotech, Inc. Process for the dissolution of copper metal
US20080175773A1 (en) * 2002-02-14 2008-07-24 Richardson H Wayne Process for the dissolution of copper metal
US6905531B2 (en) * 2002-02-14 2005-06-14 Phibro Tech, Inc. Process for the dissolution of copper metal
US6905532B2 (en) * 2002-02-14 2005-06-14 Phibro-Tech, Inc. Process for the dissolution of copper metal
US8460759B2 (en) 2003-04-09 2013-06-11 Osmose, Inc. Micronized wood preservative formulations
US8747908B2 (en) 2003-04-09 2014-06-10 Osmose, Inc. Micronized wood preservative formulations
US9079328B2 (en) 2003-04-09 2015-07-14 Koppers Performance Chemicals Inc. Micronized wood preservative formulations
US8637089B2 (en) 2003-04-09 2014-01-28 Osmose, Inc. Micronized wood preservative formulations
US8778407B2 (en) 2003-04-09 2014-07-15 Osmose, Inc. Micronized wood preservative formulations
US8747909B2 (en) 2003-04-09 2014-06-10 Osmose, Inc. Micronized wood preservative formulations
US20040258838A1 (en) * 2003-06-17 2004-12-23 Richardson H. Wayne Method for preserving wood materials using precipitated copper compounds
US8409627B2 (en) 2003-06-17 2013-04-02 Osmose, Inc. Particulate wood preservative and method for producing the same
US8871277B2 (en) 2003-06-17 2014-10-28 Osmose, Inc. Particulate wood preservative and method for producing the same
US20040258768A1 (en) * 2003-06-17 2004-12-23 Richardson H. Wayne Particulate wood preservative and method for producing same
US20050171369A1 (en) * 2003-11-19 2005-08-04 Pasek Eugene A. Methods for producing copper ethanolamine solutions
US7273944B2 (en) 2003-11-19 2007-09-25 Arch Chemicals, Inc. Methods for producing copper ethanolamine solutions
WO2005051961A1 (en) * 2003-11-19 2005-06-09 Arch Chemicals, Inc. Methods for producing copper ethanolamine solutions
AU2004293437B2 (en) * 2003-11-19 2010-10-28 Arch Chemicals, Inc. Methods for producing copper ethanolamine solutions
CN1882595B (en) * 2003-11-19 2011-06-08 阿奇化工公司 Methods for producing copper ethanolamine solutions
US8722198B2 (en) 2004-05-17 2014-05-13 Osmose, Inc. Method of preserving wood by injecting particulate wood preservative slurry
US8158208B2 (en) 2004-05-17 2012-04-17 Osmose, Inc. Method of preserving wood by injecting particulate wood preservative slurry
US20060062926A1 (en) * 2004-05-17 2006-03-23 Richardson H W Use of sub-micron copper salt particles in wood preservation
US9314030B2 (en) 2004-05-17 2016-04-19 Koppers Performance Chemicals Inc. Particulate wood preservative and method for producing same
EP1640463A1 (en) 2004-09-10 2006-03-29 Phibro-Tech, Inc. Process for the dissolution of copper metal
US20060078686A1 (en) * 2004-10-08 2006-04-13 Hodge Robert L Penetration of copper-ethanolamine complex in wood
US9775350B2 (en) 2004-10-14 2017-10-03 Koppers Performance Chemicals Inc. Micronized wood preservative formulations in organic carriers
US7566357B2 (en) 2005-04-20 2009-07-28 Phibro Wood, LLC Method of producing fine-particle copper powders
US7517382B2 (en) 2005-04-20 2009-04-14 Gang Zhao Production of fine particle copper powders
US20070213228A1 (en) * 2005-04-20 2007-09-13 Gang Zhao Method of producing fine-particle copper powders
US20060236813A1 (en) * 2005-04-20 2006-10-26 Gang Zhao Production of fine particle copper powders
US20070207076A1 (en) * 2006-03-06 2007-09-06 Osmose Inc. Method of preparing metal-containing wood preserving compositions

Also Published As

Publication number Publication date
MXPA04007806A (en) 2005-08-15
AU2003216260B2 (en) 2009-04-02
EP1490375A2 (en) 2004-12-29
US20050034563A1 (en) 2005-02-17
DE60327061D1 (en) 2009-05-20
CA2476643C (en) 2011-11-22
CN1633438A (en) 2005-06-29
ATE427952T1 (en) 2009-04-15
WO2003069025A3 (en) 2003-12-31
EP1490375A4 (en) 2006-09-13
EP1490375B1 (en) 2009-04-08
CA2476643A1 (en) 2003-08-21
AU2003216260A1 (en) 2003-09-04
US6905532B2 (en) 2005-06-14
WO2003069025A2 (en) 2003-08-21
US6905531B2 (en) 2005-06-14
US20030162986A1 (en) 2003-08-28
CN1633438B (en) 2010-05-12
US20040191143A1 (en) 2004-09-30

Similar Documents

Publication Publication Date Title
US6646147B2 (en) Process for the dissolution of copper metal
EP1640463B2 (en) Process for the dissolution of copper metal
SU1447273A3 (en) Method of producing manganese sulfate solution
CN100515944C (en) Method for regenerating sodium cyanide from solutions containing cyanogen and thiocyanate
AU2004293437B2 (en) Methods for producing copper ethanolamine solutions
WO2007053252A1 (en) Method of preparing metal-containing wood preserving compositions
US20070207076A1 (en) Method of preparing metal-containing wood preserving compositions
US20080175773A1 (en) Process for the dissolution of copper metal
US11102980B2 (en) Method of preparing copper-containing wood preserving compositions
CN112266095A (en) Method for oxidative degradation of cyanide in wastewater
WO2012051469A1 (en) Ammoniacal copper zinc arsenate concentrates and methods of preparation

Legal Events

Date Code Title Description
AS Assignment

Owner name: PHIBROTECH, INC., SOUTH CAROLINA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:RICHARDSON, HUGH W.;ZHAO, GANG;REEL/FRAME:012796/0854

Effective date: 20020401

STCF Information on status: patent grant

Free format text: PATENTED CASE

AS Assignment

Owner name: WELLS FARGO FOOTHILL, INC., GEORGIA

Free format text: SECURITY INTEREST;ASSIGNOR:PHIBRO-TECH, INC.;REEL/FRAME:014669/0244

Effective date: 20031021

AS Assignment

Owner name: WELLS FARGO FOOTHILL, INC., CALIFORNIA

Free format text: AMENDMENT NUMBER ONE TO PATENT SECURITY AGREEMENT;ASSIGNOR:PHIBRO-TECH, INC.;REEL/FRAME:018148/0478

Effective date: 20060814

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: OSMOSE, INC,NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PHIBROTECH, INC.;PHIBROWOOD, LLC;REEL/FRAME:023937/0585

Effective date: 20091006

Owner name: OSMOSE, INC, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PHIBROTECH, INC.;PHIBROWOOD, LLC;REEL/FRAME:023937/0585

Effective date: 20091006

FPAY Fee payment

Year of fee payment: 8

AS Assignment

Owner name: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLAT

Free format text: INTELLECTUAL PROPERTY SECURITY AGREEMENT;ASSIGNOR:OSMOSE, INC. (FORMERLY OSMOSE WOOD PRESERVING, INC.);REEL/FRAME:028158/0611

Effective date: 20120504

AS Assignment

Owner name: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLAT

Free format text: INTELLECTUAL PROPERTY SECURITY AGREEMENT;ASSIGNOR:OSMOSE, INC.;REEL/FRAME:029351/0791

Effective date: 20121126

AS Assignment

Owner name: PHIBRO-TECH, INC., NEW JERSEY

Free format text: RELEASE OF SECURITY INTEREST;ASSIGNOR:WELLS FARGO FOOTHILL, INC.;REEL/FRAME:033217/0042

Effective date: 20091006

AS Assignment

Owner name: WELLS FARGO BANK, NATIONAL ASSOCIATION, NEW YORK

Free format text: PATENT, TRADEMARK AND COPYRIGHT SECURITY AGREEMENT;ASSIGNORS:KOPPERS INC.;KOPPERS HOLDINGS INC.;KOPPERS DELAWARE, INC.;AND OTHERS;REEL/FRAME:033591/0020

Effective date: 20140815

AS Assignment

Owner name: OSMOSE, INC., NEW YORK

Free format text: RELEASE OF SECURITY INTERST IN INTELLECTUAL PROPERTY;ASSIGNOR:CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT;REEL/FRAME:033645/0778

Effective date: 20140815

Owner name: OSMOSE, INC. (FORMERLY OSMOSE WOOD PRESERVING, INC

Free format text: RELEASE OF SECURITY INTEREST IN INTELLECTUAL PROPERTY;ASSIGNOR:CREDIT SUISSE AG, CAYMAND ISLANDS BRANCH, AS COLLATERAL AGENT;REEL/FRAME:033645/0796

Effective date: 20140815

AS Assignment

Owner name: KOPPERS PERFORMANCE CHEMICALS INC, PENNSYLVANIA

Free format text: CHANGE OF NAME;ASSIGNOR:OSMOSE, INC.;REEL/FRAME:034036/0363

Effective date: 20140915

AS Assignment

Owner name: KOPPERS PERFORMANCE CHEMICALS INC., PENNSYLVANIA

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE REMOVE PATENT NUMBER 8221797 PREVIOUSLY RECORDED AT REEL: 034036 FRAME: 0363. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF NAME;ASSIGNOR:OSMOSE, INC.;REEL/FRAME:034563/0407

Effective date: 20140915

FPAY Fee payment

Year of fee payment: 12

AS Assignment

Owner name: PNC BANK, NATIONAL ASSOCIATION, PENNSYLVANIA

Free format text: PATENT, TRADEMARK AND COPYRIGHT SECURITY AGREEMENT;ASSIGNORS:KOPPERS, INC.;KOPPERS HOLDINGS INC.;KOPPERS DELAWARE, INC.;AND OTHERS;REEL/FRAME:043920/0523

Effective date: 20170217

AS Assignment

Owner name: KOPPERS INC. (F/K/A KOPPERS INDUSTRIES, INC.), PENNSYLVANIA

Free format text: RELEASE OF PATENT SECURITY INTERESTS;ASSIGNOR:PNC BANK, NATIONAL ASSOCIATION;REEL/FRAME:060390/0207

Effective date: 20220617

Owner name: KOPPERS UTILITY AND INDUSTRIAL PRODUCTS INC. (F/K/A COX INDUSTRIES, INC.), SOUTH CAROLINA

Free format text: RELEASE OF PATENT SECURITY INTERESTS;ASSIGNOR:PNC BANK, NATIONAL ASSOCIATION;REEL/FRAME:060390/0207

Effective date: 20220617

Owner name: KOPPERS PERFORMANCE CHEMICALS INC. (F/K/A OSMOSE, INC.), GEORGIA

Free format text: RELEASE OF PATENT SECURITY INTERESTS;ASSIGNOR:PNC BANK, NATIONAL ASSOCIATION;REEL/FRAME:060390/0207

Effective date: 20220617

Owner name: KOPPERS DELAWARE, INC., PENNSYLVANIA

Free format text: RELEASE OF PATENT SECURITY INTERESTS;ASSIGNOR:PNC BANK, NATIONAL ASSOCIATION;REEL/FRAME:060390/0207

Effective date: 20220617

AS Assignment

Owner name: OSMOSE UTILITIES SERVICES, INC., GEORGIA

Free format text: RELEASE (REEL 033591 / FRAME 0020);ASSIGNOR:WELLS FARGO BANK, NATIONAL ASSOCIATION;REEL/FRAME:060448/0192

Effective date: 20220627

Owner name: KOPPERS PERFORMANCE CHEMICALS NEW ZEALAND LIMITED (F/K/A OSMOSE NEW ZEALAND), NEW ZEALAND

Free format text: RELEASE (REEL 033591 / FRAME 0020);ASSIGNOR:WELLS FARGO BANK, NATIONAL ASSOCIATION;REEL/FRAME:060448/0192

Effective date: 20220627

Owner name: KOPPERS INC. (F/K/A KOPPERS INDUSTRIES, INC), PENNSYLVANIA

Free format text: RELEASE (REEL 033591 / FRAME 0020);ASSIGNOR:WELLS FARGO BANK, NATIONAL ASSOCIATION;REEL/FRAME:060448/0192

Effective date: 20220627

Owner name: KOPPERS PERFORMANCE CHEMICALS INC. (F/K/A OSMOSE, INC.), GEORGIA

Free format text: RELEASE (REEL 033591 / FRAME 0020);ASSIGNOR:WELLS FARGO BANK, NATIONAL ASSOCIATION;REEL/FRAME:060448/0192

Effective date: 20220627

Owner name: KOPPERS DELAWARE, INC. (F/K/A KOPPERS INDUSTRIES OF DELAWARE, INC.), PENNSYLVANIA

Free format text: RELEASE (REEL 033591 / FRAME 0020);ASSIGNOR:WELLS FARGO BANK, NATIONAL ASSOCIATION;REEL/FRAME:060448/0192

Effective date: 20220627